Production of heterocyclic dithiophosphate ether esters



United States Patent PRODUCTION OF HETEROCYCLIC DITHIO- PHOSPHATE ETHER ESTERS William M. Lanham, Charleston, W. Va., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Application January 17, 1956 Serial No. 559,545

12 Claims. (Cl. 260-461) pecially it concerns the production of a novel class of ether esters having structures corresponding to the formula wherein R, R R R R and R respectively, represents a member of the class consisting of hydrogen and the alkyl radicals, preferably those having 1 to 20 carbon atoms; X represents a member of the class consisting of oxygen and sulfur; R represents a member of the class consisting of the alkyl, cycloalkyl, haloalkyl, alkylmercaptoalkyl, alkoxyalkyl, aryloxyalkyl, aryl, haloaryl, aralkyl and alkaryl radicals; and n is 0 or 1, and m is 0 or 1.

The novel compounds of this invention have utility as plasticizers for various vinyl resins, particularly polymers and copolymers of vinyl chloride such as vinyl chloride-vinyl acetate resinous copolymers containing around 95% or more vinyl chloride in the polymer.

The novel compounds of this invention can be produced by reacting a hydrocarbon-substituted heterocyclic dithiophosphoric acid of the formula wherein R, R R R R, R and n have the meanings hereinbefore indicated, with an olefinically singly unsaturated ether or thioether having a structure represented by the formula wherein X and R respectively, have the meanings here inbefore indicated, and m is 0 or 1.

The reaction can be conducted at temperatures within the range from about -20 C. to about 150 C. However, it is preferred to use temperatures within the range from 25 C.-to 100 C. in order to avoid or minimize product losses by decomposition at the higher temperatures. Usually one of the reactants is fed dropwise in small successive portions to a solution or a suspension of the other reactant in an inert solvent or diluent. However, the two reactants may be mixed together at the outset, with or without the presence of sucha solvent or diluent, the reactants then being mixed preferably in the 2,892,863 Patented June 30, 1959 7 molar ratios of from 0.5 to 1 to 3 to 1 of the unsaturated ether reactant to the phosphorus-containing reactant.

If desired, the reaction can be conducted in the presence as catalyst of an aliphatic tertiary amine such as triethylamine, or an anhydrous alkali metal hydroxide or carbonate can be used, although the use of a catalyst is not necessary. When the unsaturated ether reactant is highly reactive a polymerization inhibitor of well known type, such as hydroquinone, preferably is used.

As previously stated, the reaction usually is conducted in the presence of an inert solvent or diluent, particularly when one or both of the reactants are solids. Useful solvents include saturated esters of the fatty acid series, such as ethyl acetate, amyl acetate, methyl propionate, and the methyl and ethyl butyrates; ketones such as acetone and methyl isobutyl ketone; ethers such as dioxane; aromatic compounds such as benzene, toluene, the xylenes, and nitrobenzene; and chlorinated solvents such as carbon tetrachloride, chloroform and chlorobenzene.

The novel products of the invention can be recovered from the reaction mixture by fractionally distilling the latter under high vacuum to remove any unreacted starting material, solvent and by-products. However, if .desired, the reaction mixture can first be washed with an aqueous solution of sodium bicarbonate or the equivalent to neutralize the reaction mixture after which it is Washed with water and the washed product stripped of unreacted materials and solvent by distillation under high vacuum. The desired product is recovered in good purity as a still residue.

Among unsaturated ethers useful in the process may be mentioned vinyl methyl ether, vinyl butyl ether, vinyl tetradecyl ether, vinyl cyclohexyl ether, vinyl 2-chloroethyl ether, vinyl 2-chloroisopropyl ether, vinyl 2-bromoethyl ether, vinyl 2-ethoxyethyl ether, vinyl 2-butoxyethy1 ether, vinyl 2-(2-methoxyethoxy)ethyl ether, allyl ethyl ether, allyl butyl ether, vinyl phenyl ether, vinyl benzyl ether, vinyl o-tolyl ether, vinyl o-xylyl ether, vinyl naphthyl ether, vinyl p-chlorophenyl ether, vinyl p-bromophenyl ether, vinyl 2-phenoxyethyl ether, allyl p-chloro- 1 phenyl ether, allyl p-nitrophenyl ether, and the corresponding thioethers, such as vinyl methyl thioether, CH =CHSCH vinyl butyl thioether, vinyl decyl thioether, vinyl 2,3-dichloropropyl thioether, vinyl ethoxyethyl thioether, vinyl phenyl thioether, vinyl benzyl thioether, vinyl tolyl thioether, and allyl butyl thioether.

The following equation illustrates the reaction involved when equimolar proportions of the reactants are reacted:

with the following ethylenically unsaturated ethers and thioethers, the compounds indicated in the table are 1; produced. i

The heterocyclic' dithiophosphoric-acid-"starting"rnaterials can be produced by reactinggphosphorus'pentasulfide" with an alkane-LZ-diol or an alkane-l,3-diol at tempera= tures within the range from 25 C. to 100 C. and above, preferably in the presence of an inert solvent for the diol and reaction products, and removing the by-product hy-'.

drogen sulfide as it is formed. Such a process is described in my pending application, Serial No. 387,064, filed October 19, 1953.

The following examples serve to illustrate the invention.

Example 1 To an agitated suspension of 68grams (0.3 moi-lof- ,5 -diethyl-2-mercapto-2-thiono l,3,2-dioxaphosphorinane' in 200 grams of toluene maintained at- 25 30 C.; there were added dropwise during 22 minutes-29"grams' (0.4 mol) of-ethyl vinyl ether. Afterstirring'the reaw tion mixture an additional 2 hours at 25 C. and st'anding overnight the mixture was stripped by distillation to a kettle temperature of 90 C. under less than 4 mm. of mercury pressure. Thus was secured in 97% yield the 5,5-diethyl 2 (2-ethoxyethylmercapto)-2-thiono-l,3,2- dioxaphosphorinane as a brown liquid residue having the following 1 propertiesz-molecular weight (ebullioscopic) follows, in percent by Weight: P=10.63 (theory=10.38');

S=23.5 (theory=2l.4 8); C=42.76 (theory=44.26); H 144 (theory=7.76).

C2115 CHr-O S;

\C I l SCHzCHqOCHaCH ofizficnro Example 2 During 15 .'-minutes62.5 grams 0.4 mol) of vinyl 2-ethylhexyl ether was added dropwise to 60 grams (0.25

mol) of 5-ethyl 2-mercapto-4-propy1=2-thiono-1,3,2-dioX-' the phosphorus-containing reactant, was secured;

CH -O' s To an agitated suspension of 68 grams (0.3 mol) of 5,5 diethyl 2 mercapto 2 thiono 1,3,2 dioxaphosphorinane in :200 grams of toluene held at 25 C. there' were added-during 20 minutes 40 grams (0.3 mol),ovinyl 2-ethylmercaptoethyl ether containing 0.05 of itsweight of phenyldieth'an'olamine as inhibitor. After-three additional'hours at 25 strippedby distillation to a kettle temperature of- C. under-1ess than 2 mm. of mercury, yielding 5,5-diethyl- 2- [-2 (2 ethylmercaptoethoxy)ethylmercapto] 2 thiono-l,3,2-dioxaphosphorinane as a light brown liquid residue having the following properties: it =1.5367; molecular weight (ebullioscopic)=361.9 359.5); and the following analysis, in percent by weight: P-8.77 (theory=8.52); C=43.70 (theory=43.'44); H: 7.69 (theory=7.58); 8:26.83 (theory=26.'75).

CgHs CHr-O S ll PSCHQCHO CHjCHISCjHi GHQ-0 Example 4 During 3 minutes 6.5 grams (0.061 mol) of vinyl 2-chloroethyl ether were added dropwise to a solution of 15 grams (0.0706 mol) of 2-mercapto-4,4,5,5-tetramethyl- 2-thiono-1,3,2-dioxaphospholane in 100 grams of benzene maintained at 40 C. After holding the reaction mixture at 25 C. overnight and then for 6.75 hours at 40 C., it was neutralized with concentrated aqueous sodium bicarbonate solutiomwashed with-water to remove the sodium salt ;of the excess 'phosphorus-containing-reactant, dried over calcium sulfate, filtered, and the filtrate stripped by distillation to a kettle temperature of 70 C. under less" than 2 mm. of mercury. The resultant 2-[2-(2-chloroethoxy) ethylmercap't'o'] -4,4 ,5 ,5 -tetran1ethy1-2-thiono- 1 ,3 ,2- dioxaphospholane', in the form of a pale green solid having the following properties, was secured in 62% yield (based on therether reactant): M.P. =5258 C.;'salt content=nil.' It had the following analysis, in percent by weight: P10.06 (theory=9.72);- Cl= 10.70 (the ory=':11.12);. (#3829 (theory=37.69); PI 6.30 (theory=6.-32'); S="20.5 (theory='20.12).

CH3 0a. -0 s rsomo mocruomci I om no Hi I C. the reaction mixture was- (theory:

Example 1 To an agitated suspension of 68 grams (0.3 mol) of 5,5-diethyl-2-mercapto-Z-thiono-1,3,2-dioxaphosphorinane .in 200 grams of toluene held at C. there were addeddropwise during 50 minutes 40 grams (0.4 mol) of vinyl isobutyl ether. After 2 hours further agitation at 25 C.,

and standing overnight, the reaction mixture was stripped by distillationto a kettle temperature of 90 C; under less than 4 mm. of mercury. A 97% yield of 5,5-diethyl- 2-(2-isobutoxyethylmercapto) -2-thiono-l,3,2 dioxaphosphorinane in the form of a clear brown fluid residue was secured having the following analysis, in percent by Example 6 To an agitated suspension of 56.5 grams (0.25 mol) of 5,5-diethyl 2-mercapto-2-thiono-1,3,2-dioxaphosphorinane in 150 grams of toluene held at 25 C. there were added dropwise during 5 minutes 57.5 grams (0.4 mol) of vinyl 2-butoxyethyl ether. After agitating at 25 C. for 2 additional hours and standing overnight at 25 C., the reaction mixture was stripped by distillation to a kettle temperature of 50 C. under less than 2 mm. of mercury. The resultant residue was further stripped in a falling film type still at 64 C. and then at 78 C. under less than 0.2 mm. of mercury, providing a 90% yield of 5,5- diethyl-2-[2-(2-butoxyethoxy) ethylmercaptol-Z-thiono-l, 3,2-dioxaphosphorinane as a clear brown liquid residue having the following properties: n =l.508O; analysis, in per cent by weight: P=8.72; S==l6.7; 0:48.92; H= 8.37.

CHr-O C1411; CHg-O The invention is susceptible of modification within the scope of the appended claims.

I claim:

1. As new compounds, heterocyclic ether esthers of dithiophosphoric acid, said ether esters having structures corresponding to the formula wherein R, R R R R and R respectively, designates a member of the class consisting of hydrogen and the lower alkyl radicals; X designates a member of the class consisting of oxygen and sulfur; R designates a member of the class consisting of the alkyl, cyclohexyl, halogensubstituted lower alkyl, lower alkyl mercaptoethyl, lower alkoxyethyl, phenyl, tolyl, xylyl, benzyl, naphthyl, phenoxyethyl, halogen-substituted phenyl, lower alkyl-substituted phenyl and phenyl-substituted lower alkyl radicals; and m and n, respectively, is of the class consisting of 0 and 1.

2. As new compounds, heterocyclic ether esters of dithiophosphoric acid, said esters having structures corresponding to the formula R wherein R, R R R R and R respectively, designates a member of the class consisting of hydrogen and the lower alkyl radicals; X is a member of the class consisting of oxygen and sulfur; and n is of the class consisting of 0 and l.

3. As new compounds, heterocyclic ether esters of dithiophosphoric acid, said esters having structures corresponding to the formula g '12: co s C)\ /i SCH,CH X-halo lower alkyl R( n c 0 R \1 wherein R, R R R R and R respectively, designates a member of the class consisting of hydrogen and the lower alkyl radicals; X is a member of the class consisting of oxygen and sulfur; and n is of the class consisting of 0 and 1.

4. As new compounds, heterocyclic ether esters of dithiophosphoric acid, said esters having structures corresponding to the formula R1\ /R 1 \i /C PSCHgCHgX-IOWGI' alkoxyethyl wherein R, R R R R and R respectively, designates member of the class consisting of hydrogen and the lower alkyl radicals; X is a member of the class consisting of oxygen and sulfur; and n is of the class consisting of 0 and 1.

5. As new compounds, heterocyclic ether esters of dithiophosphoric acid, said esters having structures corresponding to the formula 18/ m wherein R, R R R R and R respectively, designates a member of the class consisting of hydrogen and the lower alkyl radicals; X is a member of the class consisting of oxygen and sulfur; and n is of the class consisting of 0 and 1.

6. As new compounds, heterocyclic ether esters of dithiophosphoric acid, said esters having structures corresponding to the formula R R a s /C PscH CHgX-lower alkylmercaptoethyl R4 R wherein R, R R R", R and R respectively, designates a member of the class consisting of hydrogen and the lower alkyl radicals; X is a member of the class consisting of oxygen and sulfur; and n is of the class consisting of 0 and 1.

7. Process for producing heterocyclic ether esters of dithiophosphoric acids containing phosphorus in the hetil gi s qsxd rin hwh epqil siss zma qa mp qi a uhsa'tiir'ated' ether of the XR V t me wherein m is of the class co 'isistin'g of 0 and 1, and R is a radical of the class consisting of the alkyl, cyclohexyl,

halogen-substituted lower alkyl,,- loyver.-al kyl mercaptoethyl, lower alkmgyethyl, phenyl,tolyl, xylyl, benzyl,'

v i R R5 wherein n is of the class consisting of 0 and 1; and R, R

R R R and R respectiyely, are,se lected from the 20 8 8. Process as definecl iii claix n 7, wherein the unsaturated etherreactant is a vinyl'lilkyl ether. Process asldefihed in 8, wherein' tl 1e:said ether reactafit is a vinyl-ai'yl ether. 5 10s'Process-asdefinedinclaim 8; whereinthe ether reactant is-a vinyl-haloalkyl ether.

' l1--Proces's' as "defined 'inclai1 n 8;wherein the: ether reactaptis a yinyl-alkoxyalkyl ether.

12-.--Pi'oces's as"defined-in claim 8 wherein the ether .10- .reactaiit is' a wiinyl" allgylinercaptoalkyl ether.

l-lntReferencesCited thee-file of this :patent SEES- mps w; 15 12,565,920 Hook et a1. Aug. 28, 1951 2,794,041 Norman et al May 28; 1957 j v PATENTS 1,103,577 France 25, 1955 group consisting of hydrogen and theloweralkyl radicalsm 

1. AS NEW COMPOUNDS, HETERCYCLIC ETHER ESTHERS OF DITHIOPHOSPHORIC ACID, SAID ETHER ESTERS HAVING STRUCTURES CORRESPONDING TO THR FORMULA
 7. PROCESS FOR PRODUCING HETERCYCLIC ETHER ESTERS OF DITHIOPHOSPHORIC ACIDS CONTAINING PHOSPHROUS IN THE HETEROCYCLIC RING, WHICH COMPRISES REACTING AN OLEFINICALLY UNSATURATED ETHER OF THE FORMULA CH2=CH(CH2)MXR6 WHEREIN M IS OF THE CLASS CONSISTINH OF 0 AND 1: AND R6 IS A RADICAL OF THE CLASS CONSISTING OF THE ALKY, CYCLOHEXYL, HALOGEN-SUBSTITUTED LOWER ALKYL, LOWER ALKYL MERCAPTOETHYL, LOWER ALKOXYETHYL, PHENYL, TOLYL, XYLYL, BENZYL, NAPHTHYL, PHENOZYETHYL, HALOGEN-SUBSTITUTED PHENYL, LOWER ALKYL-SUBSTURUTED PHENYL AND OHENYL-SUBSTITUTE LOWER ALKYL RADICALS, AND X IS A MEMBER OF THE CLASS CONSISTING OF OXYGEN AND SULFUR, WITH A HETEROCYCLIC DITHIOPHOSPHORIC ACID ESTER OF THE FORMULA 